Other Nitrophenols

T0114 Bioremediation Technology Services, Inc., BTS Method T0136 Calgon Carbon Oxidation Technologies, Rayox T0138 Calgon Carbon Corporation, Perox-Pure 

T0173 Commodore Applied Technologies, Inc., Solvated Electron Technology (SET) T0355 Granular Activated Carbon (GAC)—General 

T0395 Idaho Research Foundation, Inc., and White Shield, Inc., Simplot Anaerobic Biological Remediation (SABRE) 

T0812 Trans Coastal Marine Services, Bioplug/Bioconduit 

---

Organosulfur Compounds with Other Functional Groups Other Nitrophenols... 

Dinoseb ec-Butyl Dinitrophenol Dinitrophenol, 4,6-iec-Butyl Other Nitrophenols Pesticides... 

ZhObshKhim 7, 2235-9 (1937) CA 32, 72 (1938)1Complex compds or Cu ammines with picric acid and some other nitrophenols such as [CufNHOj-tQHjCNCgjOla and [Cu(NH3)J [C6Hj(N0a)20]j Both compds seem to be explosive. They are not listed in our tables 20)H.Brinzinger and H.Plessing, ZAnorgChem 235, 110-14(1937) CA 32, 2450(1938)... 

The resulting fcw values are 0.14 (pH 2), 0.19 (pH 4), and 0.89 (pH 6). Hence, in contrast to apolar and weakly polar compounds (see Problem 6.2), DNOC partitions very favorably from the gas phase into an aqueous phase. It is, therefore, not surprising that this compound as well as other nitrophenols have been found in rather high concentrations (> 1 yUg-L-1) in rainwater (Tremp et al., 1993). 

Heat of combustion and heat of formation of picric acid and of other nitrophenols. The heat of combustion of picric acid at constant volume (corrected for the nitric acid formed) is 621.2 kcal/mole and the heat of formation is 63.3 kcal/mole or 276.4 kcal/kg (Gamer and Abemethy [51]). 

Gamer and Abemethy have given the following values for heats of formation of other nitrophenols ... 

DOT CLASSIFICATION 6.1 Label KEEP AWAY FROM FOOD SAFETY PROFILE Poison by ingestion, subcutaneous, and intraperitoneal routes. Moderately toxic by skin contact. A skin and severe eye irritant. When heated to decomposition it emits toxic fumes of NOx. See also other nitrophenol entries. 

Heat of combustion and heat of formation of picric acid and other nitrophenols 490... 

Yellow. Quinones, m- and p-nitroaniline, o-nitrophenol, and many other nitrO"Compounds. [Note that some nitro-compounds often appear yellow (e.g. m-dinitrobenzene and 3, 5 -dinitro-benzoic acid), but are colourless when absolutely pure.] Iodoform. 

A brief account of aromatic substitution may be usefully given here as it will assist the student in predicting the orientation of disubstituted benzene derivatives produced in the different substitution reactions. For the nitration of nitrobenzene the substance must be heated with a mixture of fuming nitric acid and concentrated sulphuric acid the product is largely ni-dinitrobenzene (about 90 per cent.), accompanied by a little o-dinitrobenzene (about 5 per cent.) which is eliminated in the recrystallisation process. On the other hand phenol can be easily nitrated with dilute nitric acid to yield a mixture of ortho and para nitrophenols. It may be said, therefore, that orientation is meta with the... 

Uses. (9-Nitrochlorobenzene is used in the synthesis of azo dye intermediates such as o-chloroaniline (Fast YeUow G Base), i9-nitroani1ine (Fast Orange GR Base), o-anisidine (Fast Red BB Base), o-phenetidine, and (9-aminophenol (see Azo dyes). It also is used in corrosion inhibitors, pigments, and agriculture chemicals. -Nitrochlorobenzene is used principally in the production of intermediates for azo and sulfur dyes. Other uses include pharmaceuticals (qv), photochemicals, mbber chemicals (qv), and insecticides (see Insectcontroltechnology). Typical intermediates manufactured from the para isomer are -lutioaruline (Fast Red GC Base), anisidine, -aminophenol, -nitrophenol, -phenylenediamine, 2-chloro-/)-anisidine (Fast Red R Base), 2,4-dinitrochlorobenzene, and l,2-dichloro-4-nitrobenzene. 

Although this reduction is more expensive than the Bnchamp reduction, it is used to manufacture aromatic amines which are too sensitive to be made by other methods. Such processes are used extensively where selectivity is required such as in the preparation of nitro amines from dinitro compounds, the reduction of nitrophenol and nitroanthraquinones, and the preparation of aminoazo compounds from the corresponding nitro derivatives. Amines are also formed under the conditions of the Zinin reduction from aromatic nitroso and azo compounds. 

Production is by the acetylation of 4-aminophenol. This can be achieved with acetic acid and acetic anhydride at 80°C (191), with acetic acid anhydride in pyridine at 100°C (192), with acetyl chloride and pyridine in toluene at 60°C (193), or by the action of ketene in alcohoHc suspension. 4-Hydroxyacetanihde also may be synthesized directiy from 4-nitrophenol The available reduction—acetylation systems include tin with acetic acid, hydrogenation over Pd—C in acetic anhydride, and hydrogenation over platinum in acetic acid (194,195). Other routes include rearrangement of 4-hydroxyacetophenone hydrazone with sodium nitrite in sulfuric acid and the electrolytic hydroxylation of acetanilide [103-84-4] (196). 

Fig. 12. Plots of pseudo-first-order rate constants for the release of p-nitrophenol from L-52 and D-52 as a function of zinc ion concentration. See Table 9 for other conditions...

D i ni trophenoi (7-D i nltrophenol), Yel m onocl, prisms or needles (recryst from dil ale, w, ligr) mp 108°, also given as 104° can be prepd by nitrating 2-nitrophenol or by other methods. Volatile with steam si sol in w or cold ale sol... 

The 2,4-dinitrophenylhydrazone of patulin and other mono-2,4-dinitrophenylhydra-zones form red zones, 2-s c-butyl-4-amino-6-nitrophenol appears as a red-orange zone while dinitrophenols and their esters are colored yellow [14]. A whole range of organophosphorus pesticides do not give any reaction [12]. 

Several medical tests can determine whether you have been exposed to methyl parathion. The first medical test measures methyl parathion in your blood or measures 4-nitrophenol, which is a breakdown product of methyl parathion, in your urine. These tests are only reliable for about 24 hours after you are exposed because methyl parathion breaks down quickly and leaves your body. These tests cannot tell whether you will have harmful health effects or what those effects may be. The next medical test measures the levels of a substance called cholinesterase in your blood. If cholinesterase levels are less than half of what they should be and you have been exposed to methyl parathion, then you may get symptoms of poisoning. However, lower cholinesterase levels may also only indicate exposure and not necessarily harmful effects. The action of methyl parathion may cause lower cholinesterase levels in your red blood cells or your blood plasma. Such lowering, however, can also be caused by factors other than methyl parathion. For example, cholinesterase values may already be low in some people, because of heredity or disease. However, a lowering of cholinesterase levels can often show whether methyl parathion or similar compounds have acted on your nerves. Cholinesterase levels in red blood cells can stay low for more than a month after you have been exposed to methyl parathion or similar chemicals. For more information, see Chapters 3 and 7. 

Neurological effects related to cholinesterase depression occurred in seven children acutely exposed to methyl parathion by inhalation as well as orally and dermally (Dean et al. 1984). The children were admitted to a local hospital with signs and symptoms of lethargy, increased salivation, increased respiratory secretions, and miosis. Two of the children were in respiratory arrest. Two children died within several days of each other. All of the children had depressed plasma and erythrocyte cholinesterase levels (Table 3-2). These effects are similar to those occurring in methyl parathion intoxication by other routes (see Sections 3.2.2.4 and 3.2.3.4). Three adults exposed in the same incident had normal plasma (apart from one female) and red blood cell cholinesterase, and urinary levels of 4-nitrophenol (0.46-12.7 ppm) as high as some of the ill children. 

---